Clear personal care formulations containing quaternary ammonium compounds and other nitrogen-containing compounds

ABSTRACT

A composition formulated from a primary anionic surfactant; optionally a secondary surfactant and/or a resin; and a nitrogen-containing compound of the structural formula:  
                 
 
     wherein R is a saturated, linear, branched or cyclic alkyl or aryl group containing 12 to 22 carbon atoms, with the proviso that R contains at least 80% of a single chain length and R is not lanolin, wheat germ or other natural broad-based chain distribution oil, R 1  is a saturated or unsaturated, linear, branched or cyclic alkyl or aryl group containing 1 to 6 carbon atoms and may contain one or more hydroxyl groups, R 2  is selected from the group consisting of hydrogen, methyl, ethyl and benzyl; and A is a monovalent anion.

RELATED APPLICATIONS

[0001] This application is a continuation-in-part (CIP) application ofPCT/US99/10405, filed May 12, 1999.

FIELD OF THE INVENTION

[0002] The present invention relates to formulations containing selectedquaternary ammonium compounds that are useful for commercial products,for instance, personal care products such as hair conditioners,shampoos, skin conditioners, and the like. More particularly, thepresent invention relates to the use of selected quaternary ammoniumcompounds to make clear and thick formulations attractive and useful forcommercial products.

BACKGROUND OF THE INVENTION

[0003] Although a variety of quaternary ammonium compounds or “quats”have been used and proposed for use in personal care products, manyprior art quats have drawbacks associated therewith. For example, lightcolor and low odor are essential for obtaining customer acceptance andfor achieving stable and acceptable long-term product aestheticproperties. Indeed, there is increasing interest in obtaining personalcare product formulations which are translucent or transparent (that is,clear) liquids, even to the point of obtaining a crystal cleardispersion. The discovery of such clear compositions requires carefulidentification of proper quaternary and/or polyquaternary ammoniumcompounds, together with appropriate additives, such as surfactants andsolvents, which act together to achieve the desired appearance. Suchclear personal care products would include: hair conditioners, shampoos,skin conditioners, body washes, liquid bath soaps, facial cleansers,make-up removers, baby baths, and hand soaps.

[0004] Each of these applications presents its own complications;because the interactions between the various components of thecompositions must be considered in addition to the individual chemistryof each component. For example, consider the formulation of a combinedconditioner and shampoo composition, also known as conditioningshampoos, two-in-one shampoos, or two-in-ones. Two-in-ones containingredients that both clean and condition the hair in one applicationand are thus very time efficient. Two-in-ones, however, aretraditionally pearlescent or opaque because most conditioningingredients, for example, quaternary ammonium compounds, are not solublein anionic detergent carriers in the normal formulation parameters forthese products. The detergent compounds with the widest range ofcleaning properties are generally anionic (negatively charged)surfactants. Such anionic surfactants, for example, may include thealkylbenzene sulfonates, α-olefin sulfonates, sodium lauryl ethersulfates, sodium lauryl sulfates, ammonium lauryl ether sulfates, andammonium lauryl sulfates available from Witco Corporation under theWITCOLATE® and WITCONATE® trademarks. In contrast, as exemplified by thequaternary ammonium compounds discussed above, conditioners aregenerally cationic (positively charged). Thus, when the anionicdetergent ingredients and cationic conditioning ingredients are presentin the same aqueous solution, as in two-in-ones, these ingredients havea natural tendency to complex together or even precipitate out ofsolution. This complexation or dispersion usually results in apearlescent or opaque mixture which may interfere with the performanceof both the detergent compound and conditioning compound and istherefore undesirable.

[0005] Moreover, it has been heretofore difficult to solubilize resins,e.g. anionic resins, in such prior art hair care formulations. Suchresins typically require heat to ring open and reveal the anioniccharge. Furthermore, it is extremely difficult to formulate these typesof resins with cationic surfactants at all, let alone obtain clearformulations using these resins.

[0006] UK Patent No. 2 160 421 relates to a conditioning and softeningcomposition that includes certain quaternary ammonium compounds. All ofthe examples prepared by this reference include coconut diethanolamide;a well-known thickening agent or viscosity-enhancing agent. The instantinvention does not require diethanolamide or other conventionalthickening agents or viscosity control agents, since the instantinvention provides a clear formulation with a high viscosity from thecomponents specified.

[0007] EP 0 511 652 A1 relates to a hair shampoo-conditioner formulationincluding an anionic cleansing surfactant, a polymeric cationicconditioning compound, a cationic conditioning surfactant, a fattyester, and water. In contrast to the formulations of the instantinvention, which are clear and have high viscosities, the compositionsof EP 0 511 652 A1 are all opaque to pearlescent formulations (Examples1 and 3-10), often with low viscosities. In addition, the compositionsof EP 0 511 652 A1 require a polymeric cationic conditioning compound,such as quarternized guar gum, which is a conventional thickening agentthat is not a required aspect of the instant invention, and ispreferably excluded from the instant invention.

[0008] WO 97/12020 relates to a liquid laundry detergent formulationcomprising an anionic surfactant component and a quaternary ammoniumcompound component. The compositions of WO 97/12020 are not said to beclear or exhibit high viscosity and, as set forth in more detail below,formulations made according to the teachings of the Examples of WO97/12020 are not clear.

[0009] In some prior art formulations, lanolin, wheat germ and othernatural broad-based chain distribution oils are used as the quaternaryammonium compound. The use of such quaternaries is not advantageoussince the same do not build-up viscosity; therefore those quaternariescannot achieve the benefits of the present invention.

SUMMARY OF THE INVENTION

[0010] The present invention is directed to novel formulations that areparticularly useful for personal care products which include, forexample, hair conditioners, shampoos, two-in-one shampoo/conditioners,skin conditioners, body washes, liquid bath soaps, facial cleansers,make-up removers, baby baths, and hand soaps. The formulations of thepresent invention are clear and may be made thick, both of which arehighly desirable and attractive properties for personal care products.Thus, the formulations of the present invention overcome the problems inthe art discussed above, and also exhibit the properties and advantagesdescribed herein.

[0011] One aspect of the present invention comprises a clear compositionformulated from ingredients comprising:

[0012] (a) a primary anionic surfactant;

[0013] (b) optionally a secondary surfactant and/or a resin; and

[0014] (c) a nitrogen-containing compound of structural formula (1):

[0015] wherein

[0016] R is a saturated or unsaturated, linear, branched or cyclic alkylor aryl group containing 12 to 22 carbon atoms that is unsubstituted;

[0017] R₁ is a saturated or unsaturated, linear, branched or cyclicalkylene group containing 1 to 6 carbon atoms and 0 to 3 hydroxylgroups;

[0018] R₂ is selected from the group consisting of hydrogen, methyl,ethyl, and benzyl; and

[0019] A⁻ is a monovalent anion.

[0020] In the present invention, at least about 80%, and most preferablyabout 90%, of the total amount of the nitrogen-containing compoundscomprises nitrogen-containing compounds having a common R group (thatis, of the same chain length or, more preferably of the same group).Moreover, nitrogen compounds of formula (1) wherein R is equal tolanolin, wheat germ or other broad-based chain distribution oils, i.e.whole oils, are excluded from the present invention. These whole oilsare excluded because they cannot build-up viscosity; therefore thosequats cannot achieve the benefits mentioned herein.

[0021] In embodiments wherein the formulation is a two component system(binary system) comprising a primary anionic surfactant and anitrogen-containing compound of formula (1), the weight ratio of theprimary anionic surfactant to the nitrogen-containing compound is from12:1 to 1:12, with a weight ratio of the primary anionic surfactant tonitrogen-containing compound of from 8:1 to 1:8 being highly preferred.

[0022] In another preferred embodiment of the present invention, theformulation is a ternary system including the secondary surfactant orthe resin as an additional essential component. In embodiments wherein aternary formulation comprising a primary anionic surfactant, a secondarysurfactant and a nitrogen-containing compound of formula (1) isemployed, the weight ratio of secondary surfactant tonitrogen-containing compound is from 6:1 to 1:6, with a weight ratiofrom 3:1 to 1:3 being more preferred. In another embodiment, theformulation is a binary system comprising a secondary surfactant and thequaternary ammonium compound of formula (1). In this embodiment, theweight ratio of secondary surfactant to nitrogen-containing compound isfrom 12:1 to 1:12, with a weight ratio of 8:1 to 1:8 being highlypreferred.

[0023] As used herein, the term “unsubstituted” means that the groupdoes not contain any atoms other than carbon and hydrogen within thegroup.

[0024] As used herein, the term “primary anionic surfactant” is intendedto include any anionic surfactant, such as ammonium lauryl sulfate,sodium lauryl sulfate, any α-olefin sulfonate, ammonium laureth sulfate(2 or 3 moles EO), sodium laureth sulfate(2 or 3 moles EO), sodiummyristyl sulfate, sodium myristeth sulfate (1-4 moles EO),TEA-dodecylbenzene sulfonate (TEA denotes triethanolamine), TEA laurylsulfate, ammonium pareth sulfate, sodium pareth sulfate, sodium olethsulfate, linear alkyl benzene sulfonate (LAS), derivatives of any of theforgoing, and similar compounds known to those of skill in the art, andmixtures thereof.

[0025] As used herein, the term “secondary surfactant” is intended toinclude amphoteric surfactants, non-ionic surfactants, betaines,sulfosuccinates, mono- and diglycerides, glycinates, sugars andderivatives thereof, hydroxysultaines, mono- and diacetates, ethoxylatedderivatives of any of the forgoing, and similar compounds known to thoseof skill in the art, and mixtures thereof. The purpose of the secondarysurfactant, which represents an optional ingredient of the presentinvention, is to enhance the charge interaction in such a way that noprecipitation occurs. Any surfactant that accomplishes or would beexpected to accomplish this result may be used as the optional secondarysurfactant in the present invention. Although not limited to thefollowing, the hydrophobic moieties of the optional secondary surfactantmay be derived from any of the following whole oils or mixtures thereof:tallow, jojoba, palm, coconut, avocado, babassu, wheat germ, rapeseed,olive, orange, corn, linseed, neem, peanut, safflower, sesame seed,soybean, sunflower seed, and cocoa butter.

[0026] The term “resin” is used herein to denote any polymeric anionicresin, particularly a maleic acid-containing copolymer with anioniccharges, such as those sold under the tradename GANTREZ and OMNIREZ byISP, and similar resins. As stated in the background section of thisapplication, such resins typically require heat to ring open and revealthe anionic charge. Thus, a heating step to an appropriate temperatureduring mixing of the ingredients is important. The formulations of thepresent invention, which contain a resin as one of the essentialingredients, however, are proven to be compatible with anionic polymericresins without precipitation or clouding, and give a clear formulation.Moreover, the order of addition of the various components of theformulations are not important and even precipitated resin can beresolubilized in formulations according to the present invention.

[0027] Another aspect of the invention eliminates the primary anionicsurfactant. In this embodiment of the present invention, the inventiveformulation comprises the nitrogen-containing compound of formula (I)and the optional secondary surfactant and/or the resin as essentialcomponents. The weight ratio of secondary surfactant tonitrogen-containing compound in this embodiment is from 12:1 to 1:12,with a weight ratio of 8:1 to 1:8 being preferred.

[0028] Yet another aspect of the present invention comprises acomposition formulated from ingredients comprising:

[0029] (a) a primary anionic surfactant;

[0030] (b) optionally a secondary surfactant and/or resin; and

[0031] (c) a nitrogen-containing compound of the structural formula (2):

[0032] wherein

[0033] R is a saturated or unsaturated, linear, branched or cyclic alkylor aryl group containing 12 to 22 carbon atoms that is unsubstituted;and

[0034] A⁻ is a monovalent anion, with the proviso that R contains atleast 80% or more of a single chain length (or species) and R is not awhole oil.

[0035] In a preferred embodiment of the present invention, the primaryanionic surfactant is selected from the group consisting of ammoniumlauryl sulfate, sodium lauryl sulfate, an α-olefin sulfonate, ammoniumlaureth sulfate (2 or 3 moles EO), sodium laureth sulfate (2 or 3 molesEO), sodium myristyl sulfate, sodium myristeth sulfate (1-4 moles EO),TEA-dodecylbenzene sulfonate, TEA lauryl sulfate, ammonium parethsulfate, sodium pareth sulfate, sodium oleth sulfate, linear alkylbenzene sulfonate (LAS), derivatives of any of the forgoing, andmixtures thereof.

[0036] In another preferred embodiment of the present invention, theprimary anionic surfactant comprises between about 1 wt. % to about 50wt. % (expressed as actives) of the total amount of components (a),optional (b), and (c), expressed as actives. In yet another preferredembodiment of the present invention, the primary anionic surfactant (asactives) comprises between about 2 wt. % to about 25 wt. % (expressed asactives) of the total amount of components (a), optional (b), and (c),expressed as actives. In a further preferred embodiment of the presentinvention, the primary anionic surfactant (as actives) comprises betweenabout 5 wt. % to about 15 wt. % (expressed as actives) of the totalamount of components (a), optional (b), and (c), expressed as actives.

[0037] In embodiments wherein a resin is employed, the resin componentcomprises between about 0.01 wt. % to about 3.0 wt. %, more preferablybetween about 0.025 wt. % to about 1.5 wt. %, and even more preferablybetween about 0.50 wt. % to about 0.75 wt. % of the total amount ofcomponents (a), (b) and (c) expressed as actives.

[0038] In another preferred embodiment of the present invention, thesecondary surfactant, which represents an optional ingredient of thepresent invention, is selected from the group consisting ofcocamidopropyl betaine, lauramidopropyl betaine, ricinoleamidopropylbetaine, myristamidoproyl betaine, palmamidopropyl betaine,stearamidopropyl betaine, behenamidopropyl betaine, erucamidopropylbetaine, cocamidopropyl hydroxysultaine, myristamidopropylhydroxysultaine, palmamidopropyl hydroxysultaine, stearamidopropylhydroxysultaine, behenamidopropyl hydroxysultaine, erucamidopropylhydroxysultaine, disodium lauroamphodiacetate, disodiumcocamphodiacetate, disodium myristamphodiacetate, disodiumpalmamphodiacetate, disodium stearamphodiacetate, disodiumbehenamphodiacete, disodium erucamphodiacetate, sodium laurylamphoacetate, sodium cocamphoacetate, sodium cocoamphopropionate, sodiumlaurylamphopropionate, disodium lauroamphodipropionate, sodium laurylsulfosuccinate, disodium laureth sulfosuccinate, cocobetaine,laurylbetaine, myristylbetaine, stearylbetaine, behenylbetaine, PEG1-300 glyceryl cocoate, such as PEG 200 glyceryl cocoate, PEG 1-300glyceryl tallowate, PEG 1-500 hydrogenated glyceryl palmitate,coco-glucoside, lauryl glucoside, decyl glucoside, sodium xylenesulfonate, and mixtures thereof.

[0039] In another preferred embodiment of the present invention, theoptional secondary surfactant comprises between about 0.1 wt. % to about50 wt. % (expressed as actives) of the total amount of components (a),(b), and (c), expressed as actives. In yet another preferred embodimentof the present invention, the optional secondary surfactant comprisesbetween about 0.5 wt. % to about 10 wt. % (expressed as actives) of thetotal amount of components (a), (b), and (c), expressed as actives. In afurther preferred embodiment of the present invention, the optionalsecondary surfactant comprises between about 2 wt. % to about 8 wt. %(expressed as actives) of the total amount of components (a), (b), and(c), expressed as actives.

[0040] In yet another preferred embodiment of the present invention, thenitrogen-containing compound (which may be of formula (1) and/or (2))comprises between about 0.1 wt. % to about 50 wt. % (expressed asactives) of the total amount of components (a), optional (b), and (c),expressed as actives. In yet another preferred embodiment of the presentinvention, the nitrogen-containing compound comprises between about 0.5wt. % to about 20 wt. % (expressed as actives) of the total amount ofcomponents (a), optional (b), and (c), expressed as actives. In afurther preferred embodiment of the present invention, thenitrogen-containing compound comprises between about 0.75 wt. % to about10 wt. % (expressed as actives) of the total amount of components (a),optional (b), and (c), expressed as actives.

[0041] Examples of the nitrogen-containing compounds according to theinstant invention include: palmitamidopropyltrimonium chloride,behenamidopropyl trimonium chloride, cetylamidopropyltrimonium chloride,palmitamidopropyltrimonium bromide, and stearylamidopropyl methosulfate.It is again emphasized that the nitrogen-containing compounds of thepresent invention are not based on whole oils; instead they are(derived) refined from fatty acids.

[0042] In a preferred embodiment of the invention, the compositionfurther comprises a salt, the salt may be selected from the groupconsisting of sodium chloride, potassium chloride, calcium chloride,magnesium chloride, ammonium chloride, sodium bromide, potassiumbromide, calcium bromide, magnesium bromide, ammonium bromide, sodiumiodide, potassium iodide, calcium iodide, magnesium iodide, ammoniumiodide, sodium acetate, potassium acetate and mixtures thereof. The saltcomponent, if present, may be used to modify the viscosity of theresulting composition. In a further preferred embodiment of the presentinvention, the salt component comprises between about 0.2 wt. % to about50 wt. %, more preferably between about 0.4 wt. % to about 5 wt. %, andmost preferably between about 0.5 wt. % to about 3 wt. % of the totalamount of components (a), optional (b), and (c), expressed as actives.In some embodiments of the invention, the composition does not contain asignificant amount of any salts.

[0043] In certain embodiments of the present invention, the compositiondoes not contain a significant amount of any conventional thickeningagents. Indeed, conventional thickening agents which would hinder theclarity of the final product such as fatty acids, pearlescent agents andcertain alkyl amides are excluded from the present invention. The term“conventional thickening agents” as used herein means any thickeningagent or viscosity-enhancing agent known to those of skill in the art,excepting salts. Examples of such conventional thickening agentsinclude: quaternized guar gum, hydroxypropyl-substituted guar gum (suchas that available from Rhône-Poulenc Corporation under the tradenameJAGUAR® HP200), polyethylene glycol (such as that available from UnionCarbide Corporation under the tradename CARBOWAX® 20M), hydrophobicmodified hydroxyethylcellulose (such as that available from the AqualonCompany under the tradename NATROSOL® Plus), organophilic clays andalkyl amides such as cocamide DEA.

BRIEF DESCRIPTION OF THE DRAWINGS

[0044]FIG. 1 is a phase diagram illustrating the contrast between twoternary systems having components A, B, and C, wherein component A issodium laureth sulfate (SLES-2), component B is cocamidopropyl betaine(AMB 14), and component C is either a dimethyl amidopropyl amine-based(DMAPA-based) quat or cetyl trimethyl ammonium chloride (CTAC).

[0045]FIG. 2 is a phase diagram illustrating the contrast between twoternary systems having components A, B, and C, wherein component A issodium laureth sulfate (SLES-2), component B is PEG-200 hydrogenatedglyceryl palmate/PEG-7 glyceryl cocoate (LI S 80), and component C iseither a DMAPA-based quat or CTAC.

[0046]FIG. 3 is a phase diagram illustrating the contrast between twoternary systems having components A, B, and C, wherein component A isC₁₄₋₁₆ α-olefin sulfonate (AOS-PC), component B is cocamidopropylbetaine (AMB 14), and component C is either a DMAPA-based quat or CTAC.

[0047]FIG. 4 is a model phase diagram illustrating the scope of thecompositions of the present invention within the one phase and gelRegion II, showing the ranges of components A, B, and C, whereincomponent A is the primary anionic surfactant, component B is thesecondary surfactant, and component C is the nitrogen-containingcompound of the structural formula(1).

[0048]FIG. 5 is a model phase diagram illustrating the preferred scopeof the compositions of the present invention within the one phase andgel Region II, showing the ranges of components A, B, and C, whereincomponent A is the primary anionic surfactant, component B is thesecondary surfactant, and component C is the nitrogen-containingcompound of the structural formula(1).

DETAILED DESCRIPTION OF THE INVENTION

[0049] The present invention is directed to novel formulations that areparticularly useful for personal care products which include, forexample, hair conditioners, shampoos, two-in-one shampoo/conditioners,skin conditioners, body washes, liquid bath soaps, facial cleansers,make-up removers, baby baths, and hand soaps. The formulations of thepresent invention are clear and also show unexpected viscosity buildingproperties and may be made thick, both highly desirable and attractiveproperties for personal care products. The hair conditioner andtwo-in-one shampoo/conditioner formulations of the present inventionexhibit good static decay reduction of the hair tress and exceptionalconditioning feel.

[0050] Examples and experiments were conducted to illustrate the presentinvention. These examples are intended only to be illustrative of thepresent invention and are not intended to limit the present invention.The wt. % of ingredients shown in the Examples below is the amount ofthe ingredient weighed out as obtained and added to the formulation; inorder to determine the amount of each active ingredient, that is, thewt. % of that component expressed as actives (“wt. % (as actives)”), usethe percentage of the actives of that component and multiply by the wt.% given. For example, when sodium laureth sulfate (2 moles EO) (26%actives) is specified as 50.0 wt. % of the formulation, only (50.0×0.26)or 13 wt. % (as actives) of sodium laureth sulfate is present in theformulation. Although not indicated therein, each of the formulations(Formulations A-H and J-K) may have a resin component according to thepresent invention incorporated and/or solubilized therein. Suchresin-containing formulations would be clear and would form one phase ora gel. It is also within the contemplation of the present invention tosubstitute a resin in place of the secondary surfactants in FormulationsA-H and J-K. Such formulations would also be clear and exhibit theproperties mentioned herein.

EXAMPLES

[0051] Formulations A-E were prepared by measuring the individualingredients into a vessel and mixing the resulting mixture at roomtemperature until it turned clear. The C₁₆ DMAPA-based quat inFormulations A-E is palmitamidopropyltrimonium chloride. As used herein,the prefix attached to the DMAPA-based quat, for example, C₁₆ or C₁₂,designating the average number of carbon atoms in the R group of formula(1) and (2). Note that the “C₁₆” designation is not meant to imply thatall of the chain lengths are C₁₆, as commercial grade fatty acidsderived from natural sources are a mixture of various chain lengths;“C₁₆” is therefore meant to indicate the average chain length of the Rgroup. As noted below, the pH of the resulting formulations may beadjusted by the addition of, for example, sodium hydroxide or citricacid. Perfumes, preservatives, dyes and other additives may also beadded, and the amount of sodium chloride can be varied to adjust theviscosity. The term “actives”, is well-known to those of skill in theart, and denotes the amount of actual substance of interest in a givencarrier, such as water or propylene glycol, and is usually expressed inpercent. Thus, adding 1 gram of C₁₆ DMAPA-based quat solution (30%actives) contributes 0.3 grams of C₁₆ DMAPA-based quat to theformulation. FORMULATION A Ingredient Wt. % Sodium laureth sulfate 13.0(2 mole EO) (26% actives) C₁₆ DMAPA-based quat (30% actives) 1.8 PEG-200hydrogenated glyceryl 1.5 palmate/PEG-7 glyceryl cocoate (70% actives)Sodium chloride 1.0 Deionized water qs to 100

[0052] FORMULATION B Ingredient Wt. % Sodium laureth sulfate 38.46 (2mole EO) (26% actives) C₁₆ DMAPA-based quat (30% actives) 16.67Cocamidopropyl betaine 14.29 (35% actives) Deionized water qs to 100

[0053] FORMULATION C Ingredient Wt. % Sodium laureth sulfate 50.0 (2mole EO) (26% actives) C₁₆ DMAPA-based quat (30% actives) 6.6Cocamidopropyl betaine 5.1 (35% actives) Sodium chloride 1.0 Deionizedwater qs to 100

[0054] FORMULATION D Ingredient Wt. % Sodium laureth sulfate 50.0 (2mole EO) (26% actives) C₁₆ DMAPA-based quat (30% actives) 6.6Cocamidopropyl hydroxysultaine 3.75 (48% actives) Sodium chloride 1.0Deonized water qs to 100

[0055] FORMULATION E Ingredient Wt. % α-Olefin sulfonate (39% actives)33.3 C₁₆ DMAPA-based quat (30% actives) 6.6 Cocamidopropyl betaine 5.1(35% actives) Sodium chloride 1.0 Deionized water qs to 100

[0056] Formulations A-E demonstrate that various combinations of a C₁₆DMAPA-based quat, specifically, palmitamidopropyltrimonium chloride,with sulfates or sulfonates in combination with betaines,hydroxysultaines, or ethoxylated mono- and diglycerides, produce clearsystems whose viscosity may be readily adjusted.

[0057] Comparative Formulations X and Y below were made using the sameprocedure used in making Formulations A-E. COMPARATIVE FORMULATION XIngredient Wt. % Sodium laureth sulfate 50.0 (2 mole EO) (26% actives)Cetyl trimethyl ammonium chloride 8.0 (CTAC) (25% actives)Cocamidopropyl betaine 5.1 (35% actives) Sodium chloride 1.0 Deionizedwater qs to 100

[0058] COMPARATIVE FORMULATION Y Ingredient Wt. % Sodium laureth sulfate50.0 (2 mole EO) (26% actives) C₁₆ DMAPA-based quat (30% actives) 6.6Cocamidopropyl betaine 5.1 (35% actives) Sodium chloride 1.0 Deionizedwater qs to 100

[0059] Comparative Formulation X did not become clear or thick with theaddition of sodium chloride and demonstrates that a DMAPA-based quat isa critical component in a formulation possessing such properties.

[0060] Comparative Formulation Y, as made, was initially clear with upto 5% actives of the C₁₆ DMAPA-based quat. When an additional 1% activesof the C₁₆ DMAPA-based quat (3.33 grams) was added, the solution becamecloudy and then clear. When a further 1% actives of the C₁₆ DMAPA-basedquat (3.33 grams) was added to the solution, however, the solutionremained cloudy. This demonstrates that there is a unique relationshipbetween the ratio of primary anionic surfactant to secondary surfactantto DMAPA-based quat in making a clear formulation.

[0061] Formulations F-K were made to demonstrate that these clearformulations could be made with other chain lengths of DMAPA-basedquats. Three DMAPA-based quats were synthesized with various alkyl chainlengths: (1) a C₁₂ DMAPA chloride quat in water (30.56% quat activesuncorrected; liquid state); (2) a C₂₂ DMAPA chloride quat in a propyleneglycol solvent system (47.36% quat actives uncorrected; nonviscousliquid state); and (3) a C₁₈ DMAPA dimethyl sulfate quat (80% quatactives uncorrected; solid state). All three quats were formulated intoclear systems in combination with an anionic surfactant and anamphoteric surfactant or ethoxylated mono- or diglyceride. Viscositymeasurements were also taken with control Formulation I, containing noquat, to show the thickening properties of the DMAPA-based quats.FORMULATION F Ingredient Wt. % Sodium laureth sulfate 48.1 (2 mole EO)(26% actives) C₁₈ DMAPA-based DMS quat (80% 2.5 actives)Cocamidopropylbetaine 5.1 (35% actives) Deionized water 43.3 Sodiumchloride 1.0

[0062] All ingredients were combined at room temperature, the blend washeated until the quat dissolved and the formulation was even.Formulation F is clear. FORMULATION G Ingredient Wt. % Sodium laurethsulfate 48.1 (2 mole EO) (26% actives) C₂₂ DMAPA-based quat in propylene4.2 glycol (47.36% actives) Cocamidopropylbetaine 5.1 (35% actives)Deionized water 41.6 Sodium chloride 1.0

[0063] All ingredients were combined at room temperature and mixed untileven. Formulation G was slightly hazy initially, but then went clear.FORMULATION H Ingredient Wt. % Sodium laureth sulfate 48.1 (2 mole EO)(26% actives) C₁₂ DMAPA-based DMS quat 6.5 (30.56% actives)Cocamidopropylbetaine 5.1 (35% actives) Deionized water 39.3 Sodiumchloride 1.0

[0064] All ingredients were combined at room temperature and mixed untileven. Formulation H was slightly hazy initially, but then went clear.FORMULATION I Ingredient Wt. % Sodium laureth sulfate 48.1 (2 mole EO)(26% actives) Cocamidopropyl betaine (36% 5.1 actives) Deionized water45.8 Sodium chloride 1.0

[0065] Formulation I was made as a control formulation. All ingredientswere combined at room temperature, mixed until even and the resultingformulation was clear. The viscosity of the above formulations weremeasured with a Brookfield DV2 RVT viscometer (available from BrookfieldEngineering Laboratories, Inc.), Spindle #6, 10 rpm, 25° C. and theresults are shown in Table 1. TABLE 1 Formulation Viscosity (cps)Formulation F (C₁₈ DMAPA-based 19,000 quat formulation) Formulation G(C₂₂ DMAPA-based 22,100 quat formulation Formulation H (C₁₂ DMAPA-based33,300 quat formulation) Formulation I (control formulation) 300

[0066] The result presented in Table 1 is surprising, as the formulationbased on DMAPA-quats having a shorter chain length (Formulation H) has ahigher viscosity than the formulation based on DMAPA-quats having alonger chain length (e.g., Formulation G). It has been determined thatthe viscosity of a particular formulation according to the instantinvention is enhanced by using the nitrogen-containing compounds offormula (1) where the R groups have the same chain length or consist ofthe same groups. Thus, if a particular formulation according to theinvention contains nitrogen containing compounds, the viscosity willincrease as the chain length distribution decreases.

[0067] Formulations containing only the primary anionic surfactant (inthis case, SLES-2) and C₁₂, C₁₆, and C₂₂ nitrogen-containing compoundsof formula (1) according to the present invention were also prepared.From these formulations it was found that such compositions of thepresent invention (a) provide significant viscosity without the additionof salt or conventional thickening agent; (b) exhibit a rapid andsignificant increase in viscosity with the addition of salt; (c)maintain such high viscosity at elevated temperatures; (d) exhibit anincrease in viscosity with increase temperature (from 20° C. to 30° C.).

[0068] A similar formulation using a quat outside the scope of theclaimed invention (such as that sold by Witco Surfactant GmbH under thetradename REWOQUAT® RTM50) does not display any of thesecharacteristics. Moreover, the composition according to the presentinvention mitigated the skin-irritating effects of the primary anionicsurfactant and nitrogen-containing compounds of formula (1) in theformulation, which was particularly marked with the weight ratio of theprimary anionic surfactant to the nitrogen-containing compounds offormula (1) was between about 3:1 to about 1:3; preferably between about2:1 to about 1:2; more preferably between about 5:3 to about 3:5; andmost preferably between about 3:2 to about 2:3. This seems to indicatethat a complex is formed between these two components and the effectsare expected to be present in the formulations according to the instantinvention that also contain a secondary surfactant.

[0069] Additional formulations J and K were made to show that thevarious alkyl chain lengths of the DMAPA-based quats could form clearsystems in mono/diglycerides and diacetates. FORMULATION J IngredientWt. % Sodium laureth sulfate 22.2 (2 mole EO) (26% actives) C₂₂DMAPA-based quat in propylene 6.3 glycol (47.36% actives) Disodiumcocoamphodiacetate 10.0 (50% actives) Deionized water 61.5

[0070] All ingredients were combined at room temperature and mixed untileven. Formulation J was slightly hazy initially, but then went clear andis a gel. FORMULATION K Ingredient Wt. % Sodium laureth sulfate 22.2 (2mole EO) (26% actives) C₁₂ DMAPA-based quat in water 9.82 (30.56%actives) PEG-200 hydrogenated glyceryl 10.0 palmate/PEG-7 glycerylcocoate (70% actives) Deionized water 60.84

[0071] All ingredients were combined at room temperature and mixed untileven. Formulation K was slightly hazy initially, but then went clear andis slightly viscous.

[0072] Example Formulation According to WO 97/12020

[0073] In order to test the performance of the compositions of theinstant invention over the formulations prepared in WO 97/12020, theformulation A of Example III in WO 97/12020 was attempted, substitutingsimilar ingredients where the specified ingredients were not availableor particularly set forth; however, the following ingredients specifiedfor formulation A of Example III was not incorporated into theformulation because they could not be obtained, or it was unclear whatthey were: diethylenetriamine pentamethylene phosphonic acid (specifiedas 1.0 wt. %); Endo A (5000 CEVU/g) (specified as 0.05 wt. %);terephthalate based polymer (specified as 0.5 wt. %); and DC 3225C(specified as 0.04 wt. %); these unincorporated ingredients account forless than 2% of the formulation and they would not be expected to affectthe clarity or opaqueness of the final product. COMPARATIVE FOKMULATIONWO 97/12020 Ingredient used [ingredient specified in WO 97/12020 AmountBlend (if different from that used)] Wt. % used (g) A SLES-3 (WitcolateES-3) 2.0 6.0 [C₁₂₋₁₅ alkyl ethoxylated sulfate] A SLS (Witcolate WACLA) 17.0 51.0 [C₁₂₋₁₅ alkyl sulfate] A Citric Acid Anhydrous 1.0 3.0 AEthanol 1.8 5.4 A Boric Acid 2.4 7.2 A DI Water 26.16 78.48 B VARISOFT ®PATC 2.0 6.0 [palmitamidopropyltrimonium chloride] B C₁₂₋₁₄ N-methylglucamide 5.0 15.0 B Alfonic 1214 EO 4.7 [C₁₂₋₁₄ fatty 6.0 18.0 alcoholethoxylate] B Industrene 7018 [C₁₂₋₁₈ fatty acid] 11.0 33.0 BMonoethanolamine (98%) 8.8 24.0 B Sodium Hydroxide 1.0 3.0 B Propanediol14.5 43.5 B 2-Butyl-1-octanol [2-Butyl Octanol] 1.0 3.0 B UCTPolydimethylsiloxane: 0.3 0.9 T-structure branch terminus PS-410 KG[Branched Silicone] C Termanyl 300 LDX [Amylase 300 KNU/g] 0.1 0.3 CLipolase 100 L 0.15 0.45 [Lipase D96/L 100 KNU/g] C Savinase 16.0 L-typeEX 0.5 1.5 [Protease 35 g/L] C Carenzyme 4500 G 0.09 0.27 [Carenzyme5000 CEVU/g]

[0074] Blend A ingredients were combined in a vessel and heated over asteam bath to approximately 80° C. Blend B ingredients were combined ina separate vessel to form Blend A+B. The first time this Blend A+Bcooled down, the glucamide separated from the rest of the blend. TheBlend A+B was reheated in a water bath to approximately 80° C. andstirred with cooling. Blend C was added when the Blend A+B reached roomtemperature to form Blend A+B+C. The resulting Blend A+B+C (aformulation according to the teachings of WO 97/12020) is a creamy,opaque emulsion which was not clear. This is probably primarily due tothe significant proportion of fatty alcohol ethoxylate and fatty acid,where the former acts as an emulsifying agent and the latter which,along with other ingredients found in the formulation, acts as anopacifying agent and thickener.

[0075] Ternary Phase Diagrams

[0076] Six ternary phase diagrams were prepared at 23° C. to illustratethe difference in performance between a certain C₁₆ DMAPA-based quat(palmitamidopropyltrimonium chloride) and cetyl trimethyl ammoniumchloride or cetrimonium chloride (CTAC) (available from WitcoCorporation under the tradename VARISOFT® 300). These six ternary phasediagrams are presented in FIGS. 1 to 3, where each Figure contains twodiagrams. Each Figure, therefore, contains data for two separate ternarydiagrams or systems: components A and B, which are the same for the twosystems in a particular Figure, and component C, which is either the C₁₆DMAPA-based quat (in one system) or CTAC (in the other system). Thus,ternary systems 1 and 2 are illustrated in FIG. 1, ternary systems 3 and4 are illustrated in FIG. 2, and ternary systems 5 and 6 are illustratedin FIG. 3. The three components of each these systems is set forth inTable 2. TABLE 2 FIG. 1 FIG. 2 FIG. 3 INCI Name (abbreviation) 1 2 3 4 56 Sodium laureth sulfate (SLES-2) X X X X Cocamidopropyl betaine (AMB14) X X X X Trimethylamidopropyl ammonium X X X chloride (C₁₆DMAPA-based quat) Cetyl trimethyl ammonium X X X chloride (CTAC) SodiumC₁₄₋₁₆ α-olefin sulfonate X X (AOS-PC) PEG-200 hydrogenated glyceryl X Xpalmate/PEG-7 glyceryl cocoate (LI S 80)

[0077] As is typical of ternary phase diagrams, each corner of the phasediagram represents one species only (10% actives); for example, atcorner C, only the quaternary compound or quat (either 10% C₁₆DMAPA-based quat or CTAC actives) is present. Moreover, there areboundary lines that indicate phase changes for each of the six ternarysystems presented in FIGS. 1 to 3. The regions or composition ranges ofa ternary system having a single phase are indicated by the symbol 1φ.The boundary line separating the region or composition range having onephase (1φ) and the region or composition range having two phases isindicated by an arrow having a legend with the symbol 2φ and indicatingwhether the boundary line applied to the DMAPA-based quat ternary systemor the CTAC ternary system of that Figure. Additionally, any gel regionsor compositions that exist for the ternary systems are labeled and it isindicated whether such gel regions apply to the DMAPA-based quat ternarysystem or the CTAC ternary system of that Figure.

[0078] In each of the experiments used to construct the ternary phasediagrams presented in FIGS. 1 to 3, a series of samples of 10 gramsample size were prepared in 20 mL vials. The anionic surfactants of thesystems were always added last. Each sample was shaken by hand or, ifnecessary, by using a mechanical vibrator. Each sample was then putaside until the next day. The samples were then examined and theappearance of a phase boundary or gel phase or lack thereof wasdetermined and such information was used to construct each ternary phasediagram. A sample was said to be two phase (2φ) if the sample showed asignificantly bluish, turbid, or milky appearance.

[0079] It should be noted that the presence of gel or thickened phaseregions in the C₁₆ DMAPA-based quat ternary phase diagram is desirablefor formulating products such as shampoos and body washes because itallows the formulators the freedom to choose desired viscosity.

FIG. 1

[0080] As shown in Table 2, FIG. 1 contains ternary systems 1 and 2which each have sodium laureth sulfate (SLES-2), available from Lonza,Inc. under the tradename CARSONOL® SLES-2, as component A,cocamidopropyl betaine (AMB 14), available from Witco Corporation underthe tradename REWOTERIC® AMB 14, as component B, and either a C₁₆DMAPA-based quat (ternary system 1) or CTAC (ternary system 2) ascomponent C. In FIG. 1, the location of an example of a particularternary composition (A:B:C=20:10:70), is indicated, including 20 wt % ofSLES-2, 10 wt. % of AMB, and 70 wt. % of either the C₁₆ DMAPA-based quat(ternary system 1) or CTAC (ternary system 2). This particularcomposition indicated is in the two phase (2φ) region in both the C₁₆DMAPA-based quat and the CTAC phase diagrams. Turning again to FIG. 1,it can be seen that the corresponding ternary phase system of the C₁₆DMAPA-based quat is different from that of CTAC. As can be seen in FIG.1, the introduction of the DMAPA unit into the quat molecule changes theinteraction between the quat and the anionic surfactant and unexpectedlyleads to a richer phase behavior. Some important aspects of thedifference between the behavior of the C₁₆ DMAPA-based quat and CTACdiscovered during these experiments and illustrated in FIG. 1 may besummarized as follows:

[0081] a. The C₁₆ DMAPA-based quat phase diagram has a much smaller twophase (2φ) region than that of the CTAC phase diagram.

[0082] b. The C₁₆ DMAPA-based quat phase diagram has two gel phaseregions (each very viscous), while the CTAC phase diagram has none.

[0083] c. The C₁₆ DMAPA-based quat gel phases are clear.

[0084] d. The large two phase (2φ) region in the CTAC phase diagramcontrasts with the two smaller gel phases and smaller two phase (2φ)region in the C₁₆ DMAPA-based quat phase diagram.

FIG. 2

[0085] As shown in Table 2, FIG. 2 contains ternary systems 3 and 4which each have sodium laureth sulfate (SLES-2), available from Lonza,Inc. under the tradename CARSONOL® SLES-2, as component A, PEG-200hydrogenated glyceryl palmate/PEG-7 glyceryl cocoate (LI S 80),available from Witco Corporation under the tradename VARONIC® LI S 80,as component B, and either the C₁₆ DMAPA-based quat (ternary system 3)or CTAC (ternary system 4) as component C. As with FIG. 1, it can beseen that the corresponding ternary phase system of the C₁₆ DMAPA-basedquat is different from that of CTAC. As can be seen in FIG. 2, theintroduction of a DMAPA unit into the quat molecule changes theinteraction between the quat and the anionic surfactant and unexpectedlyleads to a richer behavior. Some important aspects of the differencebetween the behavior of the C₁₆ DMAPA-based quat and CTAC discoveredduring these experiments and illustrated in FIG. 2 may be summarized asfollows:

[0086] a. The C₁₆ DMAPA-based quat phase diagram has a much smaller twophase (2φ) region than that of the CTAC phase diagram.

[0087] b. The C₁₆ DMAPA-based quat phase diagram has one large viscousone phase (1φ) region.

[0088] The presence of the viscous region in the C₁₆ DMAPA-based quatternary phase diagram is desirable for formulating products such asshampoos and body washes because it allows the formulators the freedomto choose viscosity. The results showed that the thickening property forclear formulations (ternary mixtures) provided by the C₁₆ DMAPA-basedquat was unexpected and unique: this property was not found in thetraditional quats.

FIG. 3

[0089] As shown in Table 2, FIG. 3 contains ternary systems 5 and 6which each have sodium C₁₄₋₁₆ α-olefin sulfonate (AOS-PC), availablefrom Rhone-Poulenc under the tradename RHODACAL® A-246-L, as componentA, cocamidopropyl betaine (AMB 14), available from Witco Corporationunder the tradename REWOTERIC® AMB 14, as component B, and either theC₁₆ DMAPA-based quat (ternary system 5) or CTAC (ternary system 6) ascomponent C. As with FIGS. 1 and 2, it can be seen that thecorresponding ternary phase system of the C₁₆ DMAPA-based is differentfrom that of CTAC. As can be seen in FIG. 3, the introduction of theDMAPA unit into the quat molecule changes the interaction between thequat and the anionic surfactant and unexpectedly leads to a richer phasebehavior. Some important aspects of the difference between the behaviorof the C₁₆ DMAPA-based quat and CTAC discovered during these experimentsand illustrated in FIG. 3 may be summarized as follows:

[0090] a. The C₁₆ DMAPA-based quat phase diagram has a much smaller twophase (2φ) region than that of the CTAC phase diagram.

[0091] b. The C₁₆ DMAPA-based quat phase diagram has one large gel phaseregion (very viscous) while the CTAC phase diagram has none.

[0092] c. The C₁₆ DMAPA-based quat gel phase is clear. d. The large twophase (2φ) region in the CTAC phase diagram contrasts with the one gelphase and smaller two phase (2φ) region in the C₁₆ DMAPA-based quatphase diagram.

[0093] The presence of the gel phase region in the C₁₆ DMAPA-based quatternary phase diagram is desirable for formulating products such asshampoos and body washes because it allows the formulators the freedomto choose desired viscosity.

[0094] As noted above, oppositely charged species can form complexes (orion pairs) in dielectric media. Depending on the extent of this chargeinteraction, it may lead to the formation of a precipitate in stronglyinteracting systems. It is well-known in the art that quaternizedammonium surfactants strongly interact with anionic surfactants, leadingto precipitation or dispersible complexes. In either case, clear systemscannot be formulated with these surfactants. It was unexpected todiscover that a quaternized surfactant, for example, the C₁₆ DMAPA-basedquat, can thicken the anionic/amphoteric systems while remaining clear;a property not seen in the traditional quats. The unexpected propertiesof the C₁₆ DMAPA-based quat can be seen in the phase diagrams shown inFIGS. 1 to 3.

[0095] Two additional ternary phase diagrams are set forth in FIGS. 4and 5 to illustrate the range of preferred compositions according to theinstant invention. In a preferred embodiment of the present invention,the composition of the instant invention is defined as the one phase andgel regions (Region II) shown in FIG. 4, wherein the primary anionicsurfactant (Component A), the secondary surfactant (Component B), andthe nitrogen-containing compound (Component C) are present in respectiveratios that define and are within the one-phase and gel regions (RegionII). In another preferred embodiment of the invention, the compositionof the instant invention is defined as the one phase and gel regions(Region II) shown in FIG. 5, wherein the primary anionic surfactant(Component A), the secondary surfactant (Component B), and thenitrogen-containing compound (Component C) are present in respectiveratios that define and are within the one-phase gel regions (Region II).In each of FIGS. 4 and 5, Components A, B, and C are expressed as wt. %of actives.

[0096] The DMAPA-based quat compounds can be used alone or in mixturesin the formulations proposed, can be used in combination with othercompounds or additives, or used as a formulation with other compounds oradditives, depending on the intended use and the advantages anddisadvantages attendant with each alternative application method. Thecompositions as described herein exhibit a number of desirableproperties making them particularly suitable for formulation intocommercial products such as conditioners and other personal careproducts as mentioned above. Most notably, the compositions are clear,i.e., transparent or translucent. This property can be realized at avariety of concentrations of active ingredient, with or even withoutspecial solvents or coupling agents. Other properties are realized aswell. For instance, many of the compositions form a stable gel andexhibit advantageous stability, solubility, and freedom fromobjectionable color and odor.

[0097] It should be noted that the compositions of the present inventionmay be formulated without a solvent system, for example, as a solid orflake composition, or may be formulated to include water, propyleneglycol, ethanol, isopropanol, diethylene glycol, or similar solvents ormixtures thereof, as a concentrate or more dilute form, depending on theapplication. Selection of a suitable solvent for a particularapplication is well-known to those of skill in the art.

[0098] It is understood that the compositions of the present inventioncan also contain appropriate aethestic additives for a givenapplication, as would be known to those of skill in the art including,without limitation, perfumes, preservatives, silicones, and dyes.Moreover, additives may be used to adjust the chemical or physicalproperties of the formulation to a desired level. Thus, an acid, forexample, citric acid, may be used to adjust the pH of the composition toan appropriate level and sodium chloride or other salt may be used toadjust the viscosity of the composition to a desired level. Usually theadditives are present in small amounts, generally up to 2 wt. % each, toprovide the desired properties. Other compounds or additives familiar tothose of skill in the art and appropriate to a particular use may alsobe used with or formulated with the composition of the presentinvention.

[0099] It is also understood that many of the examples and claimspresented include components that are salts, that is, they include ananion and a cation. It is understood by those of skill in the art thatthe identity anion or cation of a given compound may not be crucial inthe activity of the compound for a given purpose (that is, it mayconstitute a spectator ion) and an appropriate substitute may be madetherefor. Thus, with regard to the DMAPA-based quats, the counteranionmay be, for example, chloride, bromide, methyl sulfate, ethyl sulfate,or salicylate. Similarly, the sodium ion present in many of the primaryanionic surfactants claimed and presented in the examples above may bereplaced by other cations, such as potassium ion or ammonium ion,without appreciably affecting the performance of the primary anionicsurfactant. Furthermore, with regard to the salt component that may beadded to the composition or subsequently added to the composition toobtain a desired viscosity, the term “salt” is intended to cover all ofthe compounds known to those of skill in the art to be equivalent tothose mentioned herein. Thus, it is understood that such ions may besubstituted by any other ion which is not significantly deleterious tothe desired chemical or physical properties of the overall compound inits intended use herein. It is therefore understood that such ionsubstitution is well-known in the art and all such possibilities andequivalents are intended to be embraced within the appended claims.

[0100] Sample Formulations (L-T) demonstrate the compatibility ofspecific DMAPA-based quaternaries with an anionic resin and silicon. Inaddition these formulations containing an anionic resin give superiorperformance and are clear. These formulations are prepared in the samemanner as previously described for formulations A-K. FORMULATION LIngredients Wt. % Sodium Laureth Sulfate-2 (26.5%) 50.0% DisodiumLaureth Sulfosuccinate (40%) 7.0 Cocamidopropyl betaine (35%) 6.0Glycerine (USP, 99.7%) 3.0 Monobutyl Ester of Poly(Methyl Vinyl 0.8Ether/Maleic Acid) (GANREZ A-425, ISP) PalmitamidopropyltrimoniumChloride (30%) 3.0 (VARISOFT ® PATC) Water 29.0 NaCl 1.2

[0101] FORMULATION M Ingredients Wt. % Sodium Laureth Sulfate-2 (26.5%)30.0% Disodium Laureth Sulfosuccinate (40%) 5.0 Cocamidopropyl betaine(35%) 4.0 Glycerine (USP, 99.7%) 2.0 Monobutyl Ester of Poly(MethylVinyl 0.7 Ether/Maleic Acid) (GANREZ A-425, ISP)Palmitamidopropyltrimonium Chloride (30%) 5.0 (VARISOFT ® PATC) Water52.3 Nacl 1.0

[0102] FORMULATION N Ingredients Wt. % Sodium Laureth Sulfate-2 (25.5%)29.9% Disodium Laureth Sulfosuccinate (40%) 5.0 Cocamidopropyl betaine(35%) 4.0 Glycerine (USP, 99.7%) 2.0 Vinylpyrrolidone 1.0Dimethylaminopropylmethacrylamide Copolymer (STYLEZE CC-10)Palmitamidopropyltrimonium Chloride (30%) 5.0 (VARISOFT ® PATC) Water52.1 NaCl 1.0

[0103] FORMULATION O Ingredients Wt. % Sodium Laureth Sulfate-2 (26.5%)29.8 Disodium Laureth Sulfosuccinate (40%) 5.0 Cocamidopropyl betaine(35%) 4.0 Glycerine (USP, 99.7%) 2.0 Vinylpyrrolidone 1.0Dimethylaminopropylmethacrylamide Copolymer (STYLEZE CC-10)Palmitamidopropyltrimonium Chloride (30%) 5.0 (VARISOFT ® PATC) Water51.9 Silicone (EO + PO, SILWET 7001) 0.5 NaCl 1.0

[0104] FORMULATION P Ingredients Wt. % Sodium Laureth Sulfate-2 (26.5%)29.6% Disodium Laureth Sulfosuccinate (40%) 4.9 Cocamidopropyl betaine(35%) 3.9 Glycerine (USP, 99.7%) 2.0 Vinylpyrrolidone 1.0Dimethylaminopropylmethacrylamide Copolymer (STYLEZE CC-10)Palmitamidopropyltrimonium Chloride (30%) 4.9 (VARISOFT ® PATC) Water52.6 Silicone (amino derived, SILWET A-843) 1.0 NaCl 1.0

[0105] FORMULATION Q Ingredients Wt. % Ammonium Lauryl Sulfate 30.0%Disodium Laureth Sulfosuccinate (40%) 5.0 Cocamidopropyl betaine (35%)4.0 Glycerine (USP, 99.7%) 2.0 MVE/MA Copolymer Crosslinked with 1,9-0.4 Decadiene (STABILEZE 06, ISP) Palmitamidopropyltrimonium Chloride(30%) 5.0 (VARISOFT ® PATC) Water 51.2 Dimethicone (SILWET L-45) 2.0NaC1 0.4

[0106] FORMULATION R Ingredients Wt. % Ammonium Lauryl Sulfate 30.0%Disodium Laureth Sulfosuccinate (40%) 5.0 Cocamidopropyl betaine (35%)4.0 Glycerine (USP, 99.7%) 2.0 MVE/MA Copolymer Crosslinked with 1,9-0.4 Decadiene (STABILEZE 06, ISP) Palmitamidopropyltrimonium Chloride(30%) 5.0 (VARISOFT ® PATC) Water 51.2 Silicone (amino, SILWET A-843)2.0 NaC1 0.4

[0107] FORMULATION S Ingredients Wt. % Ammonium Lauryl Sulfate 30.0%Disodium Laureth Sulfosuccinate (40%) 5.0 Cocamidopropyl betaine (35%)4.0 Glycerine (USP, 99.7%) 2.0 MVE/MA Copolymer Crosslinked with 1,9-0.4 Decadiene (STABILEZE 06, ISP) Palmitamidopropyltrimonium Chloride(30%) 5.0 (VARISOFT ® PATC) Water 51.2 Dimethicone Gum (100,000 cps) 2.0NaC1 0.4

[0108] FORMULATION T Ingredients Wt. % Ammonium Lauryl Sulfate 30.0%Disodium Laureth Sulfosuccinate (40%) 5.0 Cocamidopropyl betaine (35%)4.0 Glycerine (USP, 99.7%) 2.0 MVE/MA Copolymer Crosslinked with 1,9-0.4 Decadiene (STABILEZE 06, ISP) Palmitamidopropyltrimonium Chloride(30%) 5.0 (VARISOFT ® PATC) Water 51.2 Silicone (EO + PO, SILWET 7001)2.0 NaCl 0.4

[0109] Formulations U and V were prepared using identical ingredientswith the exception that Formulation U contained 1.8%palmitamidopropyltrimonium chloride (VARISOFT® PATC) and Formulation Vcontained 1.8% cocamidopropyl betaine. These two formulations aresummarized in Table 3 below.

[0110] What is of most interest in these formulations is the differencein aesthetics (viscosity, skin feel, etc.) and a reduction inirritation. VARISOFT® PATC by itself is an irritant in a Red Blood CellTest (RBC, a standard in-vitro method for determining irritationpotential). When the formulation contains VARISOFT® PATC, an actualimprovement of the irritation profiles of the other ingredients isobserved; a definite synergism. Formulation U would be thus classifiedas a moderate irritant, which is a significant improvement overFormulation V, which would be classified as an irritant. The abovesynergism of Formulation U is not seen with other cationic quats.

[0111] Additionally, the viscosity of the two formulations was quitedifferent. With no additional salt added, the viscosity of Formulation Uwas 1300 cps; the viscosity of Formulation V, on the other hand, wasonly 44.2 cps. The Ross-Miles foam heights were the same for bothformulations (Standard ASTM testing method for surfactants). Sheet 1Formula U Formula V Ingredients Wt. % Mass % act Wt. % Mass % act SodiumLaureth-2 Sulfate 9.98 84.98 2.6 10.04 100.7 2.6 Disodium LaurethSulfosuccunate 12.47 106.22 6.2 12.51 125.44 6.2 PEG-200 HydrogenatedGlyceryl Palmitate and PEG- 4.99 42.48 3.5 5.07 50.84 3.5 7 GlycerylCocoate Sodium Cocoamphoacetate 9.98 85.01 4.0 10.03 100.63 4.0Palmitamidopropyltrumonium Chloride 2.99 25.45 1.8 CocamidopropylBetaine 5.01 50.22 1.8 Water 59.60 507.7 57.34 575.09 851.84 1002.92

[0112] As noted above, the examples provided are intended to furtherdescribe the aspects of the present invention. The examples areillustrative only and are not to be construed as limiting the scope ofthat which is regarded as the invention. Therefore, the scope of thepresent invention is only to be limited by the following claims and theequivalents thereto.

What is claimed is:
 1. A clear composition formulated from ingredientscomprising: a primary anionic surfactant; and a nitrogen-containingcompound of the structural formula:

wherein R is a saturated or unsaturated, linear, branched or cyclicalkyl or aryl group containing 12 to 22 carbon atoms that isunsubstituted, with the proviso that R contains at least 80% of a singlechain length and R is not lanolin, wheat germ or another natural broadbased chain distribution oil; R₁ is a saturated or unsaturated, linear,branched or cyclic alkylene group containing 1 to 6 carbon atoms and 0to 3 hydroxyl groups; R₂ is selected from the group consisting ofhydrogen, methyl, ethyl, and benzyl; and A⁻ is a monovalent anion,wherein the weight ratio of said primary anionic surfactant to saidnitrogen-containing compound is from 12:1 to 1:12.
 2. The clearcomposition of claim 1, wherein said weight ratio of said primaryanionic surfactant to said nitrogen-containing compound is from 8:1 to1:8.
 3. The clear composition of claim 1, wherein the primary anionicsurfactant is selected from the group consisting of ammonium laurylsulfate, sodium lauryl sulfate, an α-olefin sulfonate, ammonium laurethsulfate (2 or 3 moles EO), sodium laureth sulfate (2 or 3 moles EO),sodium myristyl sulfate, sodium myristeth sulfate (1-4 moles EO),TEA-dodecylbenzene sulfonate, TEA lauryl sulfate, ammonium parethsulfate, sodium pareth sulfate, sodium oleth sulfate, linear alkylbenzene sulfonate, and mixtures thereof.
 4. The clear composition ofclaim 1, wherein the primary anionic surfactant comprises between about1 wt. % to about 50 wt. % of the composition.
 5. The clear compositionof claim 1, further comprising a secondary surfactant, said secondarysurfactant being present in an amount such that the weight ratio of saidsecondary surfactant to said nitrogen-containing compound is from 6:1 to1:6.
 6. The clear composition of claim 5, wherein said weight ratio ofsaid secondary surfactant to said nitrogen-containing compound is from3:1 to 1:3.
 7. The clear composition of claim 5, wherein the secondarysurfactant is selected from the group consisting of cocamidopropylbetaine, lauramidopropyl betaine, ricinoleamidopropyl betaine,myristamidopropyl betaine, palmamidopropyl betaine, stearamidopropylbetaine, behenamidopropyl betaine, erucamidopropyl betaine,cocamidopropyl hydroxysultaine, myristamidopropyl hydroxysultaine,palmamidopropyl hydroxysultaine, stearamidopropyl hydroxysultaine,behenamidopropyl hydroxysultaine, erucamidopropyl hydroxysultaine,disodium lauroamphodiacetate, disodium erucamphodiacetate, sodium laurylamphoacetate, sodium cocamphoacetate, sodium cocoamphopropionate, sodiumlaurylamphopropionate, disodium lauroamphodipropionate, sodium laurylsulfosuccinate, disodium laureth sulfosuccinate, cocobetaine,laurylbetaine, myristylbetaine, stearylbetaine, behenylbetaine, PEG1-300 glyceryl cocoate, PEG 1-300 glyceryl tallowate, PEG 1-500hydrogenated glyceryl palmitate, coco-glucoside, lauryl glucoside, decylglucoside, sodium xylene sulfonate, and mixtures thereof.
 8. The clearcomposition of claim 5, wherein the secondary surfactant comprisesbetween about 0.1 wt. % to about 50 wt. % (expressed as actives) of thetotal amount of said primary anionic surfactant, said secondarysurfactant and said nitrogen-containing compound, expressed as actives.9. The clear composition of claim 8, wherein the secondary surfactantcomprises between 0.5 wt. % to about 10 wt. % (expressed as actives) ofthe total amount of said primary anionic surfactant, said secondarysurfactant and said nitrogen-containing compound, expressed as actives.10. The clear composition of claim 1, wherein the nitrogen-containingcompound comprises between about 0.1 wt. % to about 50 wt. % (expressedas actives) of the total amount of components in said composition,expressed as actives.
 11. The clear composition of claim 10, wherein thenitrogen-containing compound comprises between 0.5 wt. % to about 20 wt.% (expressed as actives) of the total amount of components in saidcomposition, expressed as actives.
 12. The clear composition of claim11, wherein the nitrogen-containing compound comprises between about0.75 wt. % to about 10 wt. % (expressed as actives) of the total amountof components in said composition, expressed as actives.
 13. The clearcomposition of claim 1, wherein R₁ is —CH₂CH₂CH₂—.
 14. The clearcomposition of claim 1, wherein R is a saturated, linear alkyl groupcontaining 12 to 22 carbon atoms that is unsubstituted and saturated.15. The clear composition of claim 1, wherein R₂ is methyl.
 16. Theclear composition of claim 1, further comprising a salt.
 17. The clearcomposition of claim 16, wherein the salt is selected from the groupconsisting of sodium chloride, potassium chloride, calcium chloride,magnesium chloride, ammonium chloride, sodium bromide, potassiumbromide, calcium bromide, magnesium bromide, ammonium bromide, sodiumiodide, potassium iodide, calcium iodide, magnesium iodide, ammoniumiodide, sodium acetate, potassium acetate, and mixtures thereof.
 18. Theclear composition of claim 15, wherein R₁ is —CH₂CH₂CH₂—
 19. The clearcomposition of claim 5, wherein the primary anionic surfactant, thesecondary surfactant, and the nitrogen-containing compound are presentin respective ratios that define and are within the Region II of FIG. 4,the primary anionic surfactant being component A of FIG. 4, thesecondary surfactant being component B of FIG. 4, and thenitrogen-containing compound being component C of FIG.
 4. 20. The clearcomposition of claim 5, wherein the primary anionic surfactant, thesecondary surfactant, and the nitrogen-containing compound are presentin respective ratios that define and are within the Region II of FIG. 5,the primary anionic surfactant being component A of FIG. 5, thesecondary surfactant being component B of FIG. 5, and thenitrogen-containing compound being component C of FIG.
 5. 21. The clearcomposition of claim 5, further comprising a resin.
 22. The clearcomposition of claim 21, wherein said resin is a maleic acid-containingcopolymer with anionic charges.
 23. The clear composition of claim 21,wherein the resin comprises between about 0.01 wt. % to about 3.0 wt. %(expressed as actives) of the total amount of all components in saidcomposition, expressed as actives.
 24. The clear composition of claim23, wherein the resin comprises between about 0.025 wt. % to about 1.5wt. % (expressed as actives) of the total amount of all components insaid composition, expressed as actives.
 25. The clear composition ofclaim 1, further comprising a resin.
 26. The clear composition of claim25, wherein said resin is a maleic acid-containing copolymer withanionic charges.
 27. The clear composition of claim 25, wherein theresin comprises between about 0.01 wt. % to about 3.0 wt. % (expressedas actives) of the total amount of all components in said composition,expressed as actives.
 28. The clear composition of claim 27, wherein theresin comprises between about 0.025 wt. % to about 1.5 wt. % (expressedas actives) of the total amount of all components in said composition,expressed as actives.
 29. A clear composition formulated fromingredients comprising a secondary surfactant; and a nitrogen-containingcompound of the structural formula:

wherein R is a saturated or unsaturated, linear, branched or cyclicalkyl or aryl group containing 12 to 22 carbon atoms that isunsubstituted, with the proviso that R contains at least 80% of a singlechain length and R is not lanolin, wheat germ or another naturalbroad-based chain distribution oil; R₁ is a saturated or unsaturated,linear, branched or cyclic alkylene group containing 1 to 6 carbon atomsand 0 to 3 hydroxyl groups; R₂ is selected from the group consisting ofhydrogen, methyl, ethyl, and benzyl; and A⁻ is a monovalent anion,wherein the weight ratio of said secondary surfactant to saidnitrogen-containing compound is from 12:1 to 1:12.
 30. The clearcomposition of claim 29, wherein said weight ratio of said secondarysurfactant to said nitrogen-containing compound is from 8:1 to 1:8. 31.A formulation comprising at least palmitamidopropyltrimonium chlorideand a primary anionic surfactant wherein said formulation mitigatesskin-irritation, said primary anionic surfactant andpalmitamidopropyltrimonium chloride are present in a concentration toprovide a weight ratio of said anionic surfactant topalmitamidopropyltrimonium chloride of from 3:1 to 1:3.